US4476059A - Chloroacetonitrile synthesis - Google Patents
Chloroacetonitrile synthesis Download PDFInfo
- Publication number
- US4476059A US4476059A US06/509,249 US50924983A US4476059A US 4476059 A US4476059 A US 4476059A US 50924983 A US50924983 A US 50924983A US 4476059 A US4476059 A US 4476059A
- Authority
- US
- United States
- Prior art keywords
- thionyl chloride
- molar proportion
- chloroacetonitrile
- trialkylamine
- lactonitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 title abstract description 3
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000005270 trialkylamine group Chemical group 0.000 claims abstract description 7
- WOFDVDFSGLBFAC-UHFFFAOYSA-N lactonitrile Chemical compound CC(O)C#N WOFDVDFSGLBFAC-UHFFFAOYSA-N 0.000 claims abstract description 6
- JNAYPRPPXRWGQO-UHFFFAOYSA-N 2-chloropropanenitrile Chemical compound CC(Cl)C#N JNAYPRPPXRWGQO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims 1
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
Definitions
- This invention relates to 2-chloroacetonitriles and a process for preparing them.
- An object of this invention is to provide a novel process for preparing 2-chloroacetonitriles.
- Another object is to provide such a process which permits the preparation of 2-chloroacetonitriles in high yields.
- a further object is to provide such a process particularly useful for the preparation of 2-chloropropionitrile.
- 2-Hydroxyacetonitriles useful in the practice of the invention are compounds corresponding to the formula: ##STR1## wherein R is an innocuous alkyl or aryl (e.g., phenyl, naphthyl, etc.) group, i.e., a substituted or unsubstituted alkyl or aryl group containing no substituents which would interfere with the reaction. Generally R is an alkyl group containing about 1-10 carbons.
- the preferred 2-hydroxyacetonitrile is lactonitrile, i.e., a compound corresponding to the above formula in which R is methyl.
- the thionyl chloride is ordinarily used in excess of the molar equivalent amount required to react with the 2-hydroxyacetonitrile--at least about 1.2 molar proportions of thionyl chloride per molar proportion of 2-hydroxyacetonitrile generally being most desirable.
- the trialkylamine employed in the practice of the invention instead of the pyridine of the prior art may be any trialkylamine in which the alkyl groups contain about 1-6 carbons, but it is preferably triethylamine. Although larger amounts may be employed when desired, this component is ordinarily used in an amount such as to provide about one molar proportion of trialkylamine per molar proportion of 2-hydroxyacetonitrile.
- the reactants are combined in the presence of a suitable diluent, such as dichloromethane, and are reacted for a suitable time, e.g., about one hour, generally at reflux temperatures.
- a suitable diluent such as dichloromethane
- the reaction product is then worked up to isolate the desired product, which may be recovered by distillation. To obtain optimum yields it is preferred to neutralize the reaction mixture prior to workup.
- the invention is advantageous in that it leads to the production of 2-chloroacetonitriles in high yields without the undue slurry build-up and resultant processing difficulties that were encountered in the process of Davies et al.
- a suitable reaction vessel was charged with one molar proportion of distilled lactonitrile and about four molar proportions of dichloromethane, to which one molar proportion of triethylamine was added with ice bath cooling.
- the reaction mixture was cooled to 5° C. under nitrogen, and 1.2 molar proportions of thionyl chloride were added over a period of two hours while keeping the pot temperature below 25° C.
- the resulting light brown slurry was heated to reflux for one hour, and the dark brown solution thus produced was cooled and neutralized to a pH of 7 with 10% sodium hydroxide.
- the organic phase was separated and extracted with saturated sodium chloride solution, dried over anhydrous sodium sulfate, filtered, and concentrated by distillation through a four-inch Vigreaux column.
- the crude product was then purified by distillation through an Oldershaw column to afford a 90% yield of 2-chloropropionitrile, a colorless liquid distilling at 120°-125° C.
- the analytical yield was close to quantitative.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A 2-hydroxyacetonitrile is reacted with thionyl chloride in the presence of a trialkylamine and a suitable solvent to form a 2-chloroacetonitrile. In a preferred embodiment of the invention, 2-chloropropionitrile is prepared by reacting lactonitrile with an excess of thionyl chloride in the presence of triethylamine and dichloromethane.
Description
This invention relates to 2-chloroacetonitriles and a process for preparing them.
As disclosed in W. Davies et al., Journal of the Chemical Society, 1951, pp. 2595-2598, it is known that 2-chloropropionitrile can be prepared by adding thionyl chloride to a mixture of lactonitrile and pyridine. To date, this has been the best method of producing 2-chloroacetonitriles on a large scale, even though it has led to the formation of a very thick slurry and has produced an isolated yield of only 50% after two distillations. It would obviously be desirable to find a way of improving this technique so as to improve processing and provide higher yields of 2-chloroacetonitriles.
An object of this invention is to provide a novel process for preparing 2-chloroacetonitriles.
Another object is to provide such a process which permits the preparation of 2-chloroacetonitriles in high yields.
A further object is to provide such a process particularly useful for the preparation of 2-chloropropionitrile.
These and other objects are attained by reacting a 2-hydroxyacetonitrile with thionyl chloride in the presence of a trialkylamine and a solvent to form a 2-chloroacetonitrile.
2-Hydroxyacetonitriles useful in the practice of the invention are compounds corresponding to the formula: ##STR1## wherein R is an innocuous alkyl or aryl (e.g., phenyl, naphthyl, etc.) group, i.e., a substituted or unsubstituted alkyl or aryl group containing no substituents which would interfere with the reaction. Generally R is an alkyl group containing about 1-10 carbons. The preferred 2-hydroxyacetonitrile is lactonitrile, i.e., a compound corresponding to the above formula in which R is methyl.
The thionyl chloride is ordinarily used in excess of the molar equivalent amount required to react with the 2-hydroxyacetonitrile--at least about 1.2 molar proportions of thionyl chloride per molar proportion of 2-hydroxyacetonitrile generally being most desirable.
The trialkylamine employed in the practice of the invention instead of the pyridine of the prior art may be any trialkylamine in which the alkyl groups contain about 1-6 carbons, but it is preferably triethylamine. Although larger amounts may be employed when desired, this component is ordinarily used in an amount such as to provide about one molar proportion of trialkylamine per molar proportion of 2-hydroxyacetonitrile.
In the process of the invention, the reactants are combined in the presence of a suitable diluent, such as dichloromethane, and are reacted for a suitable time, e.g., about one hour, generally at reflux temperatures. The reaction product is then worked up to isolate the desired product, which may be recovered by distillation. To obtain optimum yields it is preferred to neutralize the reaction mixture prior to workup.
The invention is advantageous in that it leads to the production of 2-chloroacetonitriles in high yields without the undue slurry build-up and resultant processing difficulties that were encountered in the process of Davies et al.
The following example is given to illustrate the invention and is not intended as a limitation thereof.
A suitable reaction vessel was charged with one molar proportion of distilled lactonitrile and about four molar proportions of dichloromethane, to which one molar proportion of triethylamine was added with ice bath cooling. The reaction mixture was cooled to 5° C. under nitrogen, and 1.2 molar proportions of thionyl chloride were added over a period of two hours while keeping the pot temperature below 25° C. When the addition was complete, the resulting light brown slurry was heated to reflux for one hour, and the dark brown solution thus produced was cooled and neutralized to a pH of 7 with 10% sodium hydroxide.
The organic phase was separated and extracted with saturated sodium chloride solution, dried over anhydrous sodium sulfate, filtered, and concentrated by distillation through a four-inch Vigreaux column. The crude product was then purified by distillation through an Oldershaw column to afford a 90% yield of 2-chloropropionitrile, a colorless liquid distilling at 120°-125° C. The analytical yield was close to quantitative.
It is obvious that many variations can be made in the products and processes set forth above without departing from the spirit and scope of this invention.
Claims (4)
1. A process which comprises reacting one molar proportion of lactonitrile with at least about 1.2 molar proportions of thionyl chloride in the presence of dichloromethane and at least one molar proportion of a trialkylamine to form 2-chloropropionitrile and then neutralizing the product.
2. The process of claim 1 wherein the trialkylamine is triethylamine.
3. The process of claim 1 wherein the reaction is conducted at reflux temperatures.
4. The process of claim 1 wherein one molar proportion of lactonitrile is reacted with at least about 1.2 molar proportion of thionyl chloride at reflux temperatures in the presence of dichloromethane and about one molar proportion of triethylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/509,249 US4476059A (en) | 1983-06-30 | 1983-06-30 | Chloroacetonitrile synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/509,249 US4476059A (en) | 1983-06-30 | 1983-06-30 | Chloroacetonitrile synthesis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4476059A true US4476059A (en) | 1984-10-09 |
Family
ID=24025853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/509,249 Expired - Fee Related US4476059A (en) | 1983-06-30 | 1983-06-30 | Chloroacetonitrile synthesis |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US4476059A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000026183A1 (en) * | 1998-11-04 | 2000-05-11 | Basf Aktiengesellschaft | Improved alpha-chloronitrile production method |
| FR2844792A1 (en) * | 2002-09-19 | 2004-03-26 | Poudres & Explosifs Ste Nale | Synthesis of 2-chloropropionitrile by a two stage process using a chlorinating agent formed from phosgene followed by reaction with lactonitrile, useful in agrochemistry |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2331681A (en) * | 1941-03-22 | 1943-10-12 | American Cyanamid Co | Preparation of chloroacetonitrile |
| US3118926A (en) * | 1957-10-21 | 1964-01-21 | Abbott Lab | Preparation of gamma-chlorobutyronitrile |
| US4371705A (en) * | 1979-09-21 | 1983-02-01 | The United States Of America As Represented By The United States Department Of Energy | Synthesis of alpha-amino acids |
-
1983
- 1983-06-30 US US06/509,249 patent/US4476059A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2331681A (en) * | 1941-03-22 | 1943-10-12 | American Cyanamid Co | Preparation of chloroacetonitrile |
| US3118926A (en) * | 1957-10-21 | 1964-01-21 | Abbott Lab | Preparation of gamma-chlorobutyronitrile |
| US4371705A (en) * | 1979-09-21 | 1983-02-01 | The United States Of America As Represented By The United States Department Of Energy | Synthesis of alpha-amino acids |
Non-Patent Citations (4)
| Title |
|---|
| Davies, et al., Journal of the Chemical Society, (1951), pp. 2595 2597. * |
| Davies, et al., Journal of the Chemical Society, (1951), pp. 2595-2597. |
| Weygand/Hilgetag, "Preparative Organic Chemistry", (1972), pp. 222-223, John Wiley and Sons, N.Y. |
| Weygand/Hilgetag, Preparative Organic Chemistry , (1972), pp. 222 223, John Wiley and Sons, N.Y. * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000026183A1 (en) * | 1998-11-04 | 2000-05-11 | Basf Aktiengesellschaft | Improved alpha-chloronitrile production method |
| US6353127B1 (en) | 1998-11-04 | 2002-03-05 | Basf Aktiengesellschaft | α-chloronitriles production method |
| FR2844792A1 (en) * | 2002-09-19 | 2004-03-26 | Poudres & Explosifs Ste Nale | Synthesis of 2-chloropropionitrile by a two stage process using a chlorinating agent formed from phosgene followed by reaction with lactonitrile, useful in agrochemistry |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: ETHYL CORPORATION, A VA CORP. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:DAVIDSON, ROBERT I.;REEL/FRAME:004282/0478 Effective date: 19830627 |
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| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
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| FPAY | Fee payment |
Year of fee payment: 4 |
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| FPAY | Fee payment |
Year of fee payment: 8 |
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| AS | Assignment |
Owner name: ALBERMARLE CORPORATION, VIRGINIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ETHYL CORPORATION;REEL/FRAME:007109/0340 Effective date: 19940228 |
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| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19961009 |
|
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |